EP4153680B1 - Mélange polycarbonate à brouillage réduit - Google Patents

Mélange polycarbonate à brouillage réduit Download PDF

Info

Publication number
EP4153680B1
EP4153680B1 EP21724301.3A EP21724301A EP4153680B1 EP 4153680 B1 EP4153680 B1 EP 4153680B1 EP 21724301 A EP21724301 A EP 21724301A EP 4153680 B1 EP4153680 B1 EP 4153680B1
Authority
EP
European Patent Office
Prior art keywords
component
weight
vinyl
moulding compound
compound according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP21724301.3A
Other languages
German (de)
English (en)
Other versions
EP4153680A1 (fr
Inventor
Kristina PUPOVAC
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4153680A1 publication Critical patent/EP4153680A1/fr
Application granted granted Critical
Publication of EP4153680B1 publication Critical patent/EP4153680B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/024—Preparation or use of a blowing agent concentrate, i.e. masterbatch in a foamable composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to a thermoplastic molding compound containing polycarbonate and/or polyester carbonate, rubber-modified vinyl (co)polymer and a polyorganosiloxane masterbatch, a process for producing the molding compound and the use of the molding compound for producing moldings and the moldings produced.
  • Polycarbonate blends have been known for a long time and are used in many areas of application. By choosing the blend partners, possible additional additives and the respective proportions of the components, the properties can be varied over a wide range and thus adapted to the requirements of the component to be manufactured.
  • a large area of application is vehicle construction, especially the production of automobiles and public transport such as buses and trains.
  • the stick-slip phenomenon refers to the stick-sliding of two solid bodies moving against each other. This phenomenon occurs when a body is moved whose static friction is significantly greater than the sliding friction (kinetic friction). Creaking or squeaking is a friction-induced sound caused by relative motion resulting from the stick-slip phenomenon between boundary surfaces. The elastic deformation of the two contact surfaces stores energy that is released when the static friction exceeds the sliding friction. The release of energy creates a vibration of the surfaces, which produces audible squeaking noises in the range of 200 - 10,000 Hz, which are particularly unpleasant in the vehicle interior and are often used as an indicator of poor construction quality.
  • Various techniques to eliminate or minimize noise include: applying anti-creaking surfaces or graining, which is not possible on all surfaces, changing the part geometry (tool adjustment necessary), applying anti-creaking coating or using suitable lubricants, felt strips or foam seals (technical Realizable but with additional costs and work steps connected) or even a change of material (selection of other material pairings if possible in relation to the property profile).
  • thermoplastic molding compounds In addition to the structural approaches mentioned and a fundamental change in materials, there are therefore numerous disclosures about modifications of the thermoplastic molding compounds with various additives that are intended to reduce noise.
  • EP 2 752 454B1 discloses a thermoplastic resin composition for noise reduction containing a rubber-reinforced vinyl resin obtained by polymerizing a vinyl monomer in the presence of an ethylene- ⁇ -olefin rubber polymer having a melting point of 0° C. or higher, and a silicone oil, wherein the amount of silicone oil is related to the silicon contained in the thermoplastic resin composition is 0.15% by mass or less based on 100% by mass of the thermal resin composition.
  • EP 2 610 307A1 discloses PC compositions containing 35 - 80 parts by mass of polycarbonate, 20 - 65 parts by mass of rubber-reinforced vinyl resin which is obtained by polymerizing a vinyl monomer in the presence of an ethylene- ⁇ -olefin rubber polymer having a melting point of 0 ° C or higher, the amount of ethylene ⁇ -olefin rubber polymer, based on 100% by mass of the PC composition, is 5-30% by mass.
  • EP 2 418 246A1 discloses automotive interior parts based on thermoplastic resin compositions prepared by incorporating 0.1 - 8.0 parts by mass of a silicone oil whose kinetic viscosity at 25 ° C is 10 - 100,000 cSt, into 100 parts by mass of a rubber-reinforced vinyl resin, which is a diene rubber and an ethylene- ⁇ - Olefin rubber polymer contains, the total amount of diene rubber and ethylene- ⁇ -olefin rubber polymer being 5-30% by mass, based on 100% by mass of rubber-reinforced vinyl resin and the mass ratio of diene rubber to ethylene- ⁇ -olefin rubber polymer being 1-85 : 90 - 15.
  • WO 2019/195516 A1 discloses PC/ABS composition (A) containing a masterbatch (B) which contains one or more thermoplastic organic materials (B1), a silicone elastomer (B2) and/or an uncured organopolysiloxane polymer (B3), the masterbatch (B) containing a total of 20 to 60% by weight of the components (B2) + (B3) are contained, based on the weight of (B1) + (B2) + (B3) and a total of 0.2 to 25% by weight of crosslinked material is present in the thermoplastic elastomer composition silicone elastomer.
  • B1 thermoplastic organic materials
  • B2 a silicone elastomer
  • B3 uncured organopolysiloxane polymer
  • the masterbatch is used as a noise reduction additive to a commercially available polycarbonate/ABS composition.
  • the molding composition consists of at least 90% by weight, more preferably at least 95% by weight and most preferably 100% by weight of components A, B, C and D.
  • the polybutadiene content of the molding composition is 2 to 7% by weight.
  • Aromatic polycarbonates and/or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be produced by processes known from the literature (for the production of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and the DE-AS 1 495 626 , DE-A 2 232 877 , DE-A 2 703 376 , DE-A 2 714 544 , DE-A 3 000 610 , DE-A 3 832 396 ; for the production of aromatic polyester carbonates, e.g. b. DE-A 3 007 934 ).
  • Aromatic polycarbonates are produced e.g. B. by reacting diphenols with carbonic acid halides, preferably phosgene and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, using the phase interface process, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols. It is also possible to produce them using a melt polymerization process by reacting diphenols with, for example, diphenyl carbonate.
  • Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis(hydroxyphenyl)-C 1 -C 5 alkanes, bis(hydroxyphenyl)-C 5 -C 6 -cycloalkanes, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) -sulfoxides, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones and ⁇ , ⁇ ,-bis-(hydroxyphenyl)-diisopropyl-benzenes and their core-brominated and/or core-chlorinated derivatives.
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)cyclohexane, 1,1-bis- (4-hydroxyphenyl)-3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis(3-chloro-4-hydroxyphenyl) -propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. Particularly preferred is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol-A).
  • the diphenols can be used individually or as any mixture.
  • the diphenols are known from the literature or can be obtained using processes known from the literature.
  • Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols such as 4-[2-(2,4,4 -Trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5- Dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol.
  • the amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the
  • thermoplastic, aromatic polycarbonates have average molecular weights (weight average M w , measured by GPC (gel permeation chromatography) with a polycarbonate standard based on bisphenol A) of preferably 20,000 to 40,000 g/mol, more preferably 22,000 to 32,000 g/mol, particularly preferably 24,000 to 30,000 g /mol.
  • the preferred ranges achieve a particularly advantageous balance of mechanical and rheological properties in the compositions according to the invention.
  • thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three and more phenolic groups.
  • Both homopolycarbonates and copolycarbonates are suitable.
  • copolycarbonates according to the invention according to component A 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols to be used, of polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known ( US 3,419,634 ) and can be produced using processes known from the literature. Also suitable are copolycarbonates containing polydiorganosiloxane; The production of polydiorganosiloxane-containing copolycarbonates is, for example, in DE-A 3 334 782 described.
  • Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
  • Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of between 1:20 and 20:1 are particularly preferred.
  • a carbonic acid halide preferably phosgene
  • phosgene is also used as a bifunctional acid derivative.
  • chain terminators for the production of the aromatic polyester carbonates include their chlorocarbonate esters and the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C 1 to C 22 alkyl groups or by halogen atoms, as well as aliphatic C 2 to C 22 monocarboxylic acid chlorides into consideration.
  • the amount of chain terminators is 0.1 to 10 mol%, based on moles of diphenol in the case of phenolic chain terminators and on moles of dicarboxylic dichloride in the case of monocarboxylic acid chloride chain terminators.
  • aromatic polyester carbonates When producing aromatic polyester carbonates, one or more aromatic hydroxycarboxylic acids can also be used.
  • the aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934 ), with linear polyester carbonates being preferred.
  • branching agents which can be used are tri- or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 up to 1.0 mol% (based on dicarboxylic acid dichlorides used) or tri- or polyfunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4, 6-Dimethyl-2,4-6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)- e
  • the proportion of carbonate structural units can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
  • Both the ester and carbonate portions of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture.
  • Linear polycarbonate based on bisphenol A is preferably used as component A.
  • the rubber-modified vinyl (co)polymers which can be used according to the invention as component B contain components B1 and optionally B2.
  • the weight ratio of components B1 to B2 is at least 5:1, preferably at least 10:1, more preferably 10:1 to 30:1.
  • Component B1 can also be mixtures of rubber-modified vinyl (co)polymers, each of which fulfills the above-mentioned conditions.
  • the rubber-modified vinyl (co)polymers according to component B1 have a melt flow rate (MFR), measured according to ISO 1133 (version from 2012) at 220 ° C with a stamp load of 10 kg, preferably 2 to 15 g / 10 min, particularly preferably 3 to 10 g/10min, especially 4 to 8 g/10min.
  • MFR melt flow rate
  • the glass transition temperature is determined for all components using dynamic differential calorimetry (DSC) according to DIN EN 61006 (version from 1994) at a heating rate of 10 K/min with determination of the Tg as the midpoint temperature (tangent method). .
  • both the polymerization of the vinyl monomers according to B1.1 and the resulting vinyl (co)polymer are grafted onto the rubber-elastic graft base according to B12. Furthermore, in this reaction process, a rubber-containing phase is formed through self-organization (phase separation) which also contains phase-separated inclusions Vinyl (co)polymer consisting of the monomers according to B1.1, this rubber-containing phase being dispersed in a vinyl (co)polymer matrix made up of the monomers according to B1.1.
  • the inclusions mean that vinyl (co)polymer is embedded inside the rubber particles.
  • the vinyl (co)polymer can be chemically bound to the rubber-elastic graft base or can be enclosed in the form of unbound polymer chains. The enclosed vinyl (co)polymer cannot be removed using common solvents such as acetone.
  • the size of the rubber particles in the rubber-modified vinyl (co)polymers B1 produced in this way is adjusted via the reaction conditions such as temperature and the resulting viscosity of the polymer as well as shear, for example by stirring.
  • the average particle size D50 is the diameter above and below which 50% by weight of the particles lie. Unless expressly described otherwise in the present invention, it is determined for all components by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
  • Preferred monomers B1.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate.
  • Preferred monomers B1.1.2 are selected from at least one of the monomers acrylonitrile, butyl acrylate, maleic anhydride and methyl methacrylate. Particularly preferred monomers are B1.1.1 styrene and B1.1.2 acrylonitrile.
  • B1.1.1 is styrene and B1.1.2 is a mixture of acrylonitrile and butyl acrylate.
  • component B1 can also be mixtures of two or more rubber-modified vinyl (co)polymers.
  • mixtures of two rubber-modified vinyl (co)polymers are used. It is further preferred that the first of these rubber-modified vinyl (co)polymers is used as B.1.1.1 styrene and as B1.1.2 acrylonitrile, while in the second rubber-modified vinyl (co)polymer as B.1.1.1 styrene and A mixture of acrylonitrile and butyl acrylate is used as B1.1.2.
  • the weight ratio of the first rubber-modified vinyl (co)polymer to the second rubber-modified vinyl (co)polymer is preferably 1:1 to 10:1, more preferably 2:1 to 8:1.
  • Preferred grafting bases B1.2 are diene rubbers containing butadiene, or mixtures of diene rubbers containing butadiene or copolymers of diene rubbers containing butadiene or mixtures thereof with other copolymerizable monomers (e.g. according to B1.1.1 and B1.1.2).
  • B1.2 Pure polybutadiene rubber is particularly preferred as the graft base B1.2.
  • B1.2 is styrene-butadiene block copolymer rubber.
  • the rubber-modified vinyl (co)polymers according to component B can optionally contain further rubber particles (graft polymers) B2 grafted with vinyl monomers with a rubber-elastic core and a vinyl (co)polymer shell, preferably produced in the emulsion polymerization process.
  • further rubber particles (graft polymers) B2 grafted with vinyl monomers with a rubber-elastic core and a vinyl (co)polymer shell preferably produced in the emulsion polymerization process.
  • the grafting bases B2.2 preferably have glass transition temperatures ⁇ -30°C, more preferably ⁇ -50°C, particularly preferably ⁇ -70°C.
  • the graft base B2.2 of the graft polymers B2 generally has an average particle size (D50 value) of 0.05 to 1.00 ⁇ m, preferably 0.10 to 0.7 ⁇ m, more preferably 0.15 to 0.5 ⁇ m, and particularly preferably from 0.2 to 0.4 ⁇ m.
  • Preferred monomers B2.1.1 for the graft polymers B2 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers B2.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • EP(D)M rubbers i.e. those based on ethylene/propylene and optionally dienes, acrylate, polyurethane, silicone, chloroprene, ethylene/vinyl acetate and acrylate are suitable as the graft base B2.2 of the graft polymers B2 -Silicone composite rubbers.
  • Preferred grafting bases B2.2 are diene rubbers, preferably containing butadiene or copolymers of dienes, preferably containing butadiene, and other copolymerizable vinyl monomers (e.g. according to B2.1.1 and B2.1.2) or mixtures of one or more of the aforementioned components.
  • B2.2 is styrene-butadiene rubber, particularly preferably styrene-butadiene block copolymer rubber.
  • Particularly suitable graft polymers B2 are, for example, ABS polymers, in a preferred embodiment those which are produced in the emulsion polymerization process by redox initiation with an initiator system made of organic hydroperoxide and ascorbic acid US-P 4,937,285 getting produced.
  • ABS polymers emulsion, bulk and suspension ABS
  • the rubber-modified vinyl (co)polymers according to component B contain free vinyl (co)polymer, i.e. not chemically bound to the rubber base(s) B1.2 or B2.2 and not enclosed in the rubber particles, consisting of the monomers according to B1.1 or B2.1. This can arise due to production during the polymerization of the graft polymers B1 or B2 or can be polymerized separately and mixed with component B. It is also possible that part of the free vinyl (co)polymer in the rubber-modified vinyl (co)polymer according to component B comes from the polymers B1 or B2 themselves due to production and another part was polymerized separately and added to component B.
  • the proportion of free vinyl (co)polymer (regardless of its origin), measured as acetone-soluble proportion, in component B is, based on component B, preferably at least 20% by weight, particularly preferably at least 30% by weight. %.
  • this free vinyl (co)polymer has a weight-average molecular weight Mw of 70 to 250 kg/mol, preferably from 140 to 200 kg/mol, in particular from 150 to 180 kg/mol.
  • the weight-average molecular weight Mw of the free vinyl (co)polymer in component B is measured by gel permeation chromatography (GPC) in tetrahydrofuran against polystyrene as a standard.
  • a masterbatch is an additive for polymers to give them certain properties.
  • An additive as the actual active ingredient is encapsulated in high concentration in a carrier resin under heat. After the carrier resin has cooled, granulation usually takes place in order to obtain an easily dosed form. Additives that are liquid and therefore difficult to introduce into a polymer alone can then be mixed in easily.
  • component C1 is this carrier resin.
  • Component C1 is a copolymer containing structural units derived from an olefin and structural units derived from a polar co-monomer. Ethylene and propylene are particularly suitable as olefins and acrylic acid, acrylic acid esters, methacrylic acid esters and vinyl acetate are particularly preferred as co-monomers. Mixtures of such polyolefin copolymers can also be used.
  • a particularly suitable carrier resin (C1) is Elvaloy TM AC 1609 (Dupont), which is an ethylene acrylate copolymer.
  • the proportion of component C 1 is 40 to 80% by weight, based on component C.
  • a polysiloxane contains multiple Si-O-Si bonds that form a polymer chain, where the backbone of the polymer chain consists of - (Si-O) - repeating units.
  • An organopolysiloxane contains repeating (Si-O) units in which at least one Si atom carries at least one organic group, i.e. containing at least one carbon atom.
  • a silane is a compound derived from Si-H 4 and often contains at least one Si-C bond. Unless otherwise stated, a silane contains only one Si atom.
  • a polysiloxane includes end groups and side groups.
  • An end group is a chemical group located on a Si atom located at one end of the polymer chain.
  • a side group is a group located on an Si atom, where the Si atom is not at the end of the polymer chain.
  • an organopolysiloxane contains a mixture of the following structures: where M, D, T and Q independently represent the functionality of structural groups of organopolysiloxane.
  • M represents a monofunctional group RsSiO 1/2
  • D represents a difunctional group R2Si0 2 /2
  • T represents a trifunctional group RSi0 3 /2
  • Q represents a tetrafunctional group SO 4/2 .
  • linear organopolysiloxanes have a backbone of D units and the end groups are M units
  • branched organopolysiloxanes can, for example, have a backbone of D units starting with T and/or or Q units are interspersed.
  • a crosslinking reaction is a reaction in which two or more molecules, at least one of the molecules being a polymer, are linked together to harden the polymer.
  • a crosslinker is a compound that can produce a crosslinking reaction of a polymer.
  • the process in which the elastomer and the thermoplastic matrix are mixed and the elastomer is cured with the aid of a crosslinker (or catalyst) during the mixing process is known as dynamic vulcanization.
  • the resulting blend consisting of a thermoplastic matrix and a cross-linked (vulcanized) elastomer, is referred to as thermoplastic vulcanizate. If the crosslinked (vulcanized) elastomeric component is a silicone polymer, while the thermoplastic component is an organic non-silicone polymer, it is referred to as a thermoplastic silicone vulcanizate.
  • the proportion of component C2 is preferably 20 to 60% by weight, based on component C.
  • Diorganopolysiloxane with an average of at least two alkenyl groups per molecule (C2al)
  • the silicon-bonded organic groups of component (C2al) are independently selected from hydrocarbon or halogenated hydrocarbon groups.
  • alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl; Cycloalkyl groups such as cyclohexyl and cycloheptyl; alkenyl groups with 2 to 20 carbon atoms such as vinyl, allyl and hexenyl; aryl groups with 6 to 12 carbon atoms such as phenyl, tolyl and xylyl; aralkyl groups with 7 to 20 carbon atoms such as benzyl and phenethyl; and halogenated alkyl groups with 1 to 20 carbon atoms, such as 3,3,3-trifluoropropyl and chloromethyl.
  • alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl
  • Cycloalkyl groups such as cyclohexyl and cyclohepty
  • These groups are selected so that the diorganopolysiloxane has a glass transition temperature (or melting point) that is below room temperature so that this component forms an elastomer when cured.
  • At least 85, more preferably at least 90 mol% of the silicon-bonded organic groups in component (C2al) are methyl groups.
  • polydiorganosiloxane (C2al) can be a homopolymer, a copolymer or a terpolymer containing such organic groups.
  • examples include silicone fluids or silicone rubbers comprising dimethylsiloxy units, dimethylsiloxy units and phenylmethylsiloxy units; dimethylsiloxy units and diphenylsiloxy units; and dimethylsiloxy units, diphenylsiloxy units and phenylmethylsiloxy units, among others.
  • the molecular structure is also not critical and can be linear and/or partially branched structures, with linear dimethylsiloxy units being preferred.
  • Examples include ⁇ , ⁇ -vinyldimethylsiloxy polydimethylsiloxane, an ⁇ , ⁇ vinyldimethylsiloxy copolymer of methylvinylsiloxane and dimethylsiloxane units and/or an ⁇ , ⁇ -trimethylsiloxy copolymer of methylvinylsiloxane and dimethylsiloxane units.
  • the diorganopolysiloxane polymer (C2al) may have a viscosity of at least 100,000 mm 2 s -1 (cSt) at 25 °C, but typically at least 1,000,000 mm 2 -s -1 (cSt) at 25 °C, measured using an AR 2000 rheometer from TA Instruments of New Castle, DE, USA or a suitable Brookfield viscometer with the spindle most suitable for the viscosity to be measured.
  • the diorganopolysiloxane polymer (C2al) may be an unvulcanized silicone rubber (silicone rubber) characterized by a Williams plasticity value of at least 100 mm / 100, measured in accordance with ASTM D-926-08 using a Williams parallel plate plasticimeter.
  • An alternative to using Williams plasticity rubbers can also be rated according to ASTM D2240 - 03 based on their Shore A hardness, with values typically being at least 30.
  • the diorganopolysiloxane polymer (C2al) can be modified with a small amount of a non-reactive silicone such as a trimethylsilyl-terminated polydimethylsiloxane.
  • the diorganopolysiloxane polymer (C2al) is an unvulcanized silicone rubber.
  • the organopolysiloxane with at least two Si-bonded hydrogen atoms, alternatively at least three Si-bonded hydrogen atoms per molecule (C2a2) can be, for example, a low molecular weight organosilicon resin or a short or long chain organosiloxane polymer, which can be linear or cyclic.
  • the silicon-bonded organic groups of component (C2a2) are independently selected from any of the hydrocarbon or halogenated hydrocarbon groups described above in connection with diorganopolysiloxane (C2al and C2bl), including preferred embodiments thereof.
  • component (C2a2) is also not critical and can be linear, partially branched, cyclic and network structures, with linear polymers or copolymers being preferred, and this component should be used when curing components (C2al) and (C2bl). be effective.
  • (C2a2) preferably has at least three silicon-bonded hydrogen atoms per molecule capable of reacting with the alkenyl or other aliphatic unsaturated groups of the diorganopolysiloxane polymer (C2al) and the -OH groups of (C2bl).
  • the position of the silicon-bonded hydrogen in the component (C2a2) is not critical, that is, the Si-H groups can be terminal groups or side groups in non-terminal positions along the molecular chain or at both positions.
  • at least part of the respective polymer (C2al) or (C2bl) must have at least three groups with which (C2a2) molecules can react.
  • the organopolysiloxane with at least two Si-bonded hydrogen atoms, alternatively at least three Si-bonded hydrogen atoms per molecule can, for example, have the general formula: R 3 R 4 2 SiO (R 4 2 SiO) p (R 4 HSiO) q SiR 4 2 R 3 or where R 4 denotes an alkyl or aryl group with up to 10 carbon atoms and R 3 denotes a group R 4 or a hydrogen atom, p has a value of 0 to 20 and q has a value of 1 to 70 and where per molecule at least 2 or 3 silicon-bonded hydrogen atoms are present.
  • R 4 can be a lower alkyl group with 1 to 3 carbon atoms, such as a methyl group.
  • the organopolysiloxane with at least two Si-bonded hydrogen atoms, alternatively at least three Si-bonded hydrogen atoms per molecule (C2a2) can, for example, have a viscosity of 0.5 to 1000 mm 2 s -1 (cSt) at 25 ° C, preferably 2 to 100 mm 2 ⁇ s -1 (cSt) more preferably 5 to 60 mm 2 ⁇ s -1 (cSt) at 25°C, typically measured with a Brookfield viscometer and the most appropriate spindle for the viscosity range measured.
  • the average degree of polymerization of (C2a2) for example, can be in the range of 30 to 400 siloxane units per molecule.
  • (C2a2) may comprise a mixture of more than one of these materials.
  • the molar ratio of Si-H groups in (C2a2) to aliphatically unsaturated groups in the diorganopolysiloxane polymer (C2al) is preferably at least 1:1 and can be up to 8:1 or 10:1.
  • the molar ratio of Si-H groups to aliphatic unsaturated groups is preferably in the range from 1.5: 1 to 5: 1.
  • (C2a2) is used in an amount such that the molar ratio of Si-H therein to Si-OH in component (C2bl) is about 0.5 to 10, preferably 1 to 5, and most preferably about 1.5.
  • Si-H functional materials are well known in the art and many are commercially available.
  • the hydrosilylation catalyst (C2a3) is preferably a platinum group metal (platinum, ruthenium, osmium, rhodium, iridium and palladium) or a compound thereof.
  • Platinum and/or platinum compounds are preferred, for example finely powdered platinum; a chloroplatinic acid or an alcohol solution of a chloroplatinic acid; an olefin complex of a chloroplatinic acid; a complex of a chloroplatinic acid and an alkenylsiloxane; a platinum diketone complex; metallic platinum on silica, alumina, carbon or a similar support; or a thermoplastic resin powder containing a platinum compound.
  • the catalyst (C2a3) is preferably used in an amount of 0.5 to 100 ppm (by weight) of platinum group metal based on the polyorganosiloxane composition (C), more preferably 1 to 50 ppm.
  • the hydrosilylation catalyst (C2a3) catalyzes the reaction of the alkenyl groups of the diorganopolysiloxane polymer (C2al) with the Si-H groups of (C2a2).
  • an inhibitor may optionally be included in the composition to retard the curing process.
  • the term "inhibitor” herein means a material that retards the curing of the component (C2al) when incorporated in small amounts, such as less than 10 percent by weight based on the siloxane composition of (C2al), without affecting the overall curing of the to prevent mixing.
  • Inhibitors of platinum group-based catalysts are known. These include hydrazines, triazoles, phosphines, mercaptans, organic nitrogen compounds, acetylene alcohols, silylated acetylene alcohols, maleates, fumarates, ethylenically or aromatically unsaturated amides, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon monoesters and diesters, nitriles and diaziridines.
  • the inhibitor (C2a5) is preferably selected from the group consisting of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 3-butyn-1-ol, 3-butyn-2-ol, propargyl alcohol, 2-phenyl-2-propyn-1-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclopentanol, 1-phenyl-2-propynol and mixtures thereof.
  • the inhibitor (C2a5) can be added in the range of 0 to 10% by weight based on the component (C2), preferably 0.05 to 5% by weight of the component (C2), but is generally used in an amount , which is sufficient to delay the curing of the diorganopolysiloxane (C2al). This set can be optimized for a given system through routine experiments.
  • the radical initiator (C2a4) is a compound that decomposes at elevated temperature to form radical species.
  • the latter promotes the cross-linking reaction between the alkenyl groups of diorganopolysiloxanes (C2al) during the dynamic vulcanization step of the present process.
  • This component is selected, for example, from azo compounds, carbon compounds and organic peroxy compounds such as hydroperoxides, diacyl peroxides, ketone peroxides, peroxyesters, dialkyl peroxides, diaryl peroxides, arylalkyl peroxides, peroxydicarbonates, peroxyketals, peroxyacids, acylalkyls and alkyl monoperoxydicarbonates.
  • the radical initiator (C2a4) is selected so that the difference between the six minute half-life of the initiator and the process temperature is between -60 ° C and 20 ° C.
  • T (6) represents the temperature (°C) at which the initiator has a half-life of 6 Minutes
  • T (0) represents the processing temperature (°C) before the initiator addition (i.e. the actual temperature of the mixture of components (Cl) to (C2)).
  • the value of T (6) is available from the manufacturer of the initiator or can be determined by methods known in the art.
  • the temperature After introduction of the initiator, the temperature generally rises slightly
  • radical initiators examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dibenzoyl peroxide, tert-amyl peroxyacetate, 1,4-di(2-tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, 2, 4,4-Trimethylpentyl-2-hydroperoxide, diisopropylbenzene monohydroperoxide, cumyl hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, 1, 1-di (tert-butylperoxy) cyclohexane, tert-butyl peroxy) cyclohexane, tert-butyl peroxy) Peroxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane-
  • the initiator (C2a4) is used in an amount sufficient to cure the diorganopolysiloxane (C2al), and this amount is optimized for a given system through routine experimentation.
  • the initiator (C2a4) is preferably added in an amount of 0.05 to 6 parts by weight, alternatively 0.2 to 3 parts by weight, per 100 parts by weight of diorganopolysiloxane (C2al).
  • the diorganopolysiloxane (C2bl) is a silicone liquid or a silicone rubber, each terminated with silanol (ie -SiOH) groups and has a viscosity of at least 100,000 mm 2 s -1 (cSt) at 25 ° C, preferably at least 1,000,000 mm 2 s -1 (cSt) at 25 °C.
  • the silicon-bonded organic groups of component (C2bl) are independently selected from hydrocarbon or halogenated hydrocarbon groups as defined above for (C2al). Again, methyl preferably constitutes at least 85, more preferably at least 90, mole percent of the silicon-bonded organic groups in component (C2bl).
  • the polydiorganosiloxane (C2bl) may be a homopolymer, a copolymer or a terpolymer containing such organic groups.
  • examples include silicone fluids or silicone rubbers comprising dimethylsiloxy units and phenylmethylsiloxy units; dimethylsiloxy units and diphenylsiloxy units; and dimethylsiloxy units, diphenylsiloxy units and phenylmethylsiloxy units, among others.
  • the molecular structure is also not critical and can have linear or partially branched structures, with linear structures being preferred.
  • organopolysiloxane (C2bl) include: dimethylhydroxysiloxy - end-blocked dimethylsiloxane homopolymers; Dimethylhydroxysiloxy-end-blocked methylphenylsiloxane-dimethylsiloxane copolymers and dimethylhydroxysiloxy-end-blocked methylphenylpolysiloxanes.
  • Preferred systems for low temperature applications include silanol-functional methylphenylsiloxane dimethylsiloxane copolymers and diphenylsiloxane-dimethylsiloxane copolymers, with the molar content of the dimethylsiloxane units preferably being about 93%.
  • component (C2bl) can also consist of combinations of two or more organopolysiloxane liquids or gums. Most preferably, component (C2bl) is a polydimethylsiloxane homopolymer terminated with a silanol group at each end of the molecule.
  • the molecular weight of the diorganopolysiloxane is sufficient to impart a Williams plasticity number of at least about 30, as determined by ASTM D-926-08.
  • the plasticity number is defined as the thickness in millimeters ⁇ 100 of a cylindrical test specimen with a volume of 2 cm 3 and a height of approximately 10 mm after the specimen has been subjected to a compressive load of 49 for three minutes at 25 ° C Newton was exposed.
  • the plasticity number should be about 100 to 200, most preferably about 120 to 185.
  • Such uncrosslinked silicone rubbers can be easily dispersed in the one or more thermoplastic organic materials (Cl) without the need for a filler (C2c).
  • liquid diorganopolysiloxanes with a viscosity of about 10 to 100 Pa-s at 25 °C often cannot be easily dispersed in further thermoplastic resin.
  • the liquid must be mixed with up to about 300 parts by weight of filler (C2c), as described below, for every 100 parts by weight (C2bl) to facilitate dispersion.
  • C2c filler
  • the liquid and filler are mixed before this combination is added to further thermoplastic resin, but these may be added separately.
  • the condensation catalyst (C2b3) of the present invention is any compound that promotes the condensation reaction between the Si-OH groups of diorganopolysiloxane (C2bl) and the Si-H groups of the organopolysiloxane with at least two Si-bonded hydrogen atoms, preferably at least three Si-bonded hydrogen atoms per molecule (C2a2) promotes to harden the diorganopolysiloxane by forming -Si-O-Si bonds.
  • the catalyst (C2b3) cannot be a platinum compound or complex because the use of such a condensation catalyst often results in poor processing as well as poor physical properties of the resulting thermoplastic silicone vulcanizate.
  • the condensation catalyst (C2b3) is present in an amount that is sufficient to harden the diorganopolysiloxane (C2bl) and the organopolysiloxane with at least two, preferably at least three Si-bonded hydrogen atoms, (C2a2) as defined above.
  • Suitable catalysts include metal carboxylates such as dibutyltin diacetate, dibutyltin dilaurate, tin tripropyl acetate, tin octoate, tin oxalate, tin naphthanate; amines such as triethylamine, ethylenetriamine; and quaternary ammonium compounds such as benzyltrimethylammonium hydroxide, betahydroxyethyltrimethylammonium 2-ethylhexoate and betahydroxyethylbenzyltrimethyldimethylammonium butoxide (see, for example, US 3,024,210 ).
  • metal carboxylates such as dibutyltin diacetate, dibutyltin dilaurate, tin tripropyl acetate, tin octoate, tin oxalate, tin naphthanate
  • amines such as triethylamine, ethylenetriamine
  • the composition used to make the vulcanized silicone elastomer may contain a reinforcing filler (C2c).
  • the reinforcing filler (C2c) can be, for example, silicon dioxide.
  • the silica may be, for example, fumed silica, such as that sold by Cabot under the trademark Cab-O-Sil MS-75D, or it may be precipitated silica.
  • the particle size of the silica is, for example, in the range from 0.5 ⁇ m to 20 ⁇ m, preferably from 1 to 10 ⁇ m.
  • the silicon dioxide can be a surface-treated silicon dioxide.
  • the surface treatment can be carried out, for example, with a silane or with a polysiloxane.
  • the silane or polysiloxane used to treat the silica usually contains hydrophilic groups that bind to the silica surface and aliphatic unsaturated hydrocarbon or hydrocarbonoxy groups and/or Si-bonded hydrogen atoms.
  • the silica may be treated, for example, with 2 to 60% by weight, based on the silica, of an alkoxysilane containing alkenyl groups or an oligomeric organopolysiloxane containing alkenyl groups.
  • the steps mentioned are carried out in such a way as to enable the components to be heated and mixed.
  • the component (C1) must be softened. Temperatures between 185 °C and 310 °C are suitable for this.
  • Mixing can be achieved, for example, by compounding using a uniaxial extruder, a biaxial extruder or a multiaxial extruder.
  • mixing can be carried out using, for example, a batch internal mixer such as a Z-blade mixer or a Banbury mixer, ensuring sufficient mixing time to achieve an even distribution of the components.
  • the masterbatch can then be granulated.
  • the diorganopolysiloxane (C2al) or (C2bl) is metered in and distributed under mechanical mixing energy into the softened or melted matrix of the one or more thermoplastic organic materials (Cl).
  • the components of the alternative curing packages are then metered into the mixture separately (no preferred order) or in combination to initiate and complete the vulcanization of the respective polyorganosiloxane.
  • a hydrosilylation reaction inhibitor (addition cure reaction inhibitor) (C2a5) may be added to the mixture to increase the residence time before completion of the vulcanization reaction in a hydrosilylation (addition) cure process.
  • the inhibitor (C2a5) is dosed into the composition either before the catalyst and/or the crosslinker.
  • the optional additives (C2c), can be introduced simultaneously or separately as required during or after completion of the dynamic curing process.
  • predispersed organopolysiloxane compositions may be introduced into the one or more thermoplastic organic materials (Cl) at elevated temperature.
  • the components of the composition used to produce the vulcanized silicone elastomer can be premixed and cured so that the already vulcanized silicone elastomer is mixed into the one or more thermoplastic organic materials (Cl).
  • melt blending equipment is a twin screw extruder.
  • Suitable masterbatches and their production are in WO 2019/195516 A1 disclosed.
  • a suitable commercially available product is Dow Corning TM HMB-1903 Masterbatch (Dow Chemical).
  • the molding composition according to the invention can contain one or more polymer additives, preferably selected from the group consisting of anti-dripping agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis, heat aging and UV stabilizers as well Transesterification inhibitors), flowability promoters, phase compatibilizers, other polymers different from components A, B and C Components (e.g. functional blend partners), fillers and reinforcing materials as well as dyes and pigments.
  • polymer additives preferably selected from the group consisting of anti-dripping agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis, heat aging and UV stabilizers as well Transesterification inhibitors), flowability promoters, phase compatibilizers, other polymers different from components A, B and C
  • the molding composition contains at least one polymer additive selected from the group consisting of lubricants and mold release agents, stabilizers, anti-dripping agents, flowability promoters, phase compatibilizers, other polymeric components, dyes and pigments.
  • the molding compound contains as a stabilizer at least one representative selected from the group consisting of sterically hindered phenols, phosphoric acids, organic phosphites and sulfur-based co-stabilizers.
  • thermoplastic molding materials can be produced, for example, by mixing the respective ingredients (components) in a known manner and at temperatures of preferably 200 ° C to 320 ° C, particularly preferably at 220 ° C to 290 ° C, very particularly preferably at 230 ° C to 270 °C in conventional units such as internal kneaders, extruders and twin-screw screws, melt-compounded and melt-extruded. This process is generally referred to as compounding in the context of this application.
  • molding compound is therefore understood to mean the product that is obtained when the respective components are melt-compounded and melt-extruded.
  • the individual components of the molding material can be mixed in a known manner both successively and simultaneously, both at around 20 ° C (room temperature) and at a higher temperature. This means that, for example, some of the components can be metered via the main intake of an extruder and the remaining components can be fed in via a side extruder later in the compounding process.
  • the molding compositions according to the invention can be used to produce moldings of any kind. These can be produced, for example, by injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from previously produced plates or foils.
  • the molding compositions according to the invention are particularly suitable for processing in injection molding, extrusion, blow molding and deep-drawing processes. The injection molding process is most preferred.
  • moldings that can be produced from the molding material according to the invention are films, profiles, housing parts of all kinds, for example for household appliances such as juicers, coffee machines, mixers; for office machines such as monitors, flat screens, notebooks, printers, copiers; Plates, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, especially for the automotive sector.
  • household appliances such as juicers, coffee machines, mixers
  • office machines such as monitors, flat screens, notebooks, printers, copiers
  • Plates pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, especially for the automotive sector.
  • compositions and molding compounds according to the invention are also suitable for the production of the following molded bodies or molded parts: interior fittings for rail vehicles, ships, airplanes, buses and other motor vehicles, body parts for motor vehicles, housings for electrical devices containing small transformers, housings for devices for information processing and transmission, massage devices and Housings for this, toy vehicles for children, flat wall elements, housings for safety devices, heat-insulated transport containers, molded parts for sanitary and bathroom equipment, cover grilles for fan openings and housings for garden tools.
  • the molding compounds according to the invention are particularly suitable for producing housings and coverings for medical devices.
  • the molding compounds are particularly suitable for automobile parts with relative movement to one another, such as lids, shelves, pull-out cup holders, clipped-together parts such as panels, plastic parts around the seat, etc.
  • Component A is a compound having Component A:
  • Linear polycarbonate based on bisphenol-A with a weight average molecular weight Mw of 26000 g/mol (determined by GPC in methylene chloride with polycarbonate as standard).
  • Acrylonitrile (A)-butadiene (B)-styrene (S) polymer produced in the bulk polymerization process, which contains a disperse phase of rubber particles grafted with styrene-acrylonitrile copolymer based on pure polybutadiene rubber as a grafting base containing inclusions of styrene-acrylonitrile copolymer and contains a styrene-acrylonitrile copolymer matrix that is not bound to the rubber.
  • Component B-1a has an A:B:S ratio of 23:9:68% by weight and a gel content, determined as acetone-insoluble portion, of 20% by weight.
  • the tetrahydrofuran-soluble styrene-acrylonitrile copolymer in component B-1a has a weight-average molecular weight M w (measured by GPC in tetrahydrofuran as a solvent with polystyrene as a standard) of 160 kg/mol.
  • M w weight-average molecular weight
  • the melt flow rate (MFR) of component B-1a measured according to ISO 1133 (2012 version) at 220 ° C with a punch load of 10 kg, is 6.5 g / 10 min.
  • Component B-1b has an A:B:S:BA ratio of 22.5:10:63:4.5% by weight and a gel content, determined as acetone-insoluble portion, of 19% by weight.
  • the tetrahydrofuran-soluble styrene-acrylonitrile-n-butyl acrylate copolymer in component B-1b has a weight-average molecular weight M w (measured by GPC in tetrahydrofuran as a solvent with polystyrene as a standard) of 115 kg/mol.
  • the average particle size of the disperse phase D50, measured by ultracentrifugation, is 0.5 ⁇ m.
  • the melt flow rate (MFR) of component B-1b measured according to ISO 1133 (2012 version) at 220 ° C with a punch load of 10 kg, is 28 g / 10 min.
  • the rubber particles do not contain any inclusions.
  • Irganox TM B900 (mixture of 80% Irgafos TM 168 (tris(2,4-di-tert-butylphenyl) phosphite) and 20% Irganox TM 1076 (2,6-di-tert-butyl-4-( octadecanoxycarbonylethyl)phenol) (BASF).
  • Irganox TM 1076, 2,6-Di-tert-butyl-4-(octadecanoxycarbonylethyl)phenol (BASF).
  • Pentaerythritol tetrastearate as a lubricant/release agent.
  • Bayblend® T85 XF (Covestro Deutschland AG) is used in the comparative examples. This is a blend of polycarbonate and an acrylonitrile-butadiene-styrene copolymer (ABS) with a weight ratio of B1:B2 of less than 1.
  • Makrolon ® M2600 (Covestro Deutschland AG), a linear polycarbonate based on bisphenol-A with a weight-average molecular weight Mw of 26000 g/mol (determined by GPC in methylene chloride with polycarbonate as a standard) and a polymethyl methacrylate (PMMA) (Plexiglass TM 8N, Evonik Industries AG).
  • the components were mixed on a ZSK-25 twin-screw extruder from Werner & Pfleiderer at a melt temperature of 260 °C.
  • the moldings were formed at a mass temperature of 260 °C or 300 °C (for Makrolon ® M2600) and 250 °C (for Plexiglas TM 8N) and a mold temperature of 80 °C or 70 °C (for Plexiglas TM 8N). using an Arburg 270 E injection molding machine.
  • the risk priority number serves as a measure of the stick-slip tendency. It describes the tendency of a material pair that tends to stick-slip under the given conditions. RPZ can take a value from 1 to 10.
  • an RPN between 1 and 3 is to be viewed as uncritical, i.e. H. Stick-slip is not to be expected under the tested conditions.
  • an RPN of 4 to 5 the material pairing is in a limit range. Audible noise caused by the stick-slip effect cannot be ruled out.
  • the material pairing is critical with regard to the stick-slip effect and audible noise is to be expected.
  • the principle of stick-slip measurement is based on the fact that two samples are moved relative to each other under the influence of a normal force (40N) and at a predefined speed (1mm/s). This causes the selected material surfaces to “shear” against each other grated.
  • the test stand consists of a movement unit, the flat slide, and a force unit, a leaf spring equipped with a round sample carrier.
  • the slide sample (60 mm ⁇ 70 mm) and spring sample (30 mm ⁇ 50 mm) are glued on using double-sided adhesive tape.
  • the spring sample is moved forward against the slide sample with a predefined normal force using a pneumatic drive and the slide is then set into a linear oscillatory movement by an electric motor.
  • the oscillating movement of the carriage has a travel distance (testing distance) of 20 mm.
  • the alternation between sticking and sliding is responsible for the generation of stick-slip noise.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (15)

  1. Masse de moulage thermoplastique, contenant
    A) au moins un polymère choisi dans le groupe constitué par le polycarbonate et le polyestercarbonate,
    B) un polymère contenant
    B1) au moins un (co)polymère de vinyle modifié par caoutchouc contenant
    B1.1) 80 à 95% en poids, par rapport à B1, d'au moins un monomère de vinyle et
    B1.2) 5 à 20% en poids, par rapport à B1, d'une ou de plusieurs bases de greffage contenant du polybutadiène, élastiques comme du caoutchouc,
    où B1 contient
    des particules de caoutchouc contenant du polybutadiène, greffées par les monomères de vinyle B1.1, qui contiennent des inclusions de (co)polymère de vinyle constitué par les monomères de vinyle B1.1 et
    une matrice de (co)polymère de vinyle non liée à ces particules de caoutchouc et non incluse dans des particules de caoutchouc, constituée par les monomères de vinyle B1.1
    et éventuellement B2) d'autres particules de caoutchouc greffées par des monomères de vinyle, constituées par
    B2.1) 5 à 75% en poids, par rapport à B2, d'au moins un monomère de vinyle sur
    B2.2) 25 à 95% en poids, par rapport à B2, d'une ou de plusieurs bases de greffage, élastiques comme du caoutchouc,
    le rapport pondéral des composants B1 à B2 valant au moins 5:1,
    C) un lot maître solide à température ambiante contenant
    C1) un ou plusieurs copolymères contenant des motifs structuraux dérivés d'une oléfine et des motifs structuraux dérivés d'un comonomère polaire,
    C2) un élastomère de silicone vulcanisé.
  2. Masse de moulage selon la revendication 1, les particules de caoutchouc contenant du polybutadiène, greffées par les monomères de vinyle B1.1, contenues dans le composant B1 présentant un diamètre moyen de particule D50, mesuré par ultracentrifugation, de 0,5 à 1,5 µm.
  3. Masse de moulage selon la revendication 1, le composant B1 présentant une teneur en polybutadiène de 7 à 15% en poids.
  4. Masse de moulage selon l'une des revendications précédentes, le composant B1 étant préparé par un procédé de polymérisation en masse.
  5. Masse de moulage selon l'une des revendications précédentes, le composant B2 étant préparé par un procédé de polymérisation en émulsion.
  6. Masse de moulage selon l'une des revendications précédentes, la teneur en polybutadiène étant de 2 à 7% en poids, par rapport à la masse de moulage.
  7. Masse de moulage selon l'une des revendications précédentes, le composant B1 étant un mélange de deux (co)polymères de vinyle modifiés par caoutchouc et, pour le premier de ces (co)polymères de vinyle modifiés par caoutchouc, les monomères de vinyle B1.1 étant un mélange de styrène et d'acrylonitrile et, pour le deuxième de ces (co)polymères de vinyle modifiés par caoutchouc, les monomères de vinyle B1.1 étant un mélange de styrène, d'acrylonitrile et d'acrylate de butyle.
  8. Masse de moulage selon l'une des revendications précédentes, le composant C1 étant un copolymère contenant des motifs structuraux dérivés d'éthylène et d'un acrylate et la proportion de motifs structuraux dérivés d'un acrylate dans le composant C1 étant de 6 à 12% en poids.
  9. Masse de moulage selon l'une des revendications précédentes, le composant C contenant 40 à 80% en poids du composant C1 et 20 à 60% en poids du composant C2.
  10. Masse de moulage selon l'une des revendications précédentes, contenant
    50-80% en poids de composant A,
    10-40% en poids de composant B,
    1-10% en poids de composant C.
  11. Masse de moulage selon l'une des revendications précédentes, le composant C étant préparé par vulcanisation dynamique, l'élastomère de silicone vulcanisé C2 étant dispersé par un procédé de mélange dans la matrice thermoplastique C1.
  12. Masse de moulage selon l'une des revendications précédentes, contenant en outre, comme composant D, au moins un additif choisi dans le groupe constitué par les agents ignifuges, les agents lubrifiants et de démoulage, les stabilisants, les promoteurs de l'aptitude à l'écoulement, les promoteurs de compatibilité ainsi que les colorants et les pigments.
  13. Procédé pour la préparation d'une masse de moulage selon l'une des revendications 1 à 12, les composants A à C et éventuellement D étant mélangés les uns avec les autres à une température de 200 à 320°C et ensuite refroidis et granulés.
  14. Utilisation d'une masse de moulage selon l'une des revendications 1 à 13 pour la production de corps moulés.
  15. Corps moulé, pouvant être obtenu à partir d'une masse de moulage selon l'une des revendications 1 à 13.
EP21724301.3A 2020-05-18 2021-05-11 Mélange polycarbonate à brouillage réduit Active EP4153680B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20175182 2020-05-18
PCT/EP2021/062398 WO2021233727A1 (fr) 2020-05-18 2021-05-11 Mélange de polycarbonate à bruit de perturbation réduit

Publications (2)

Publication Number Publication Date
EP4153680A1 EP4153680A1 (fr) 2023-03-29
EP4153680B1 true EP4153680B1 (fr) 2024-02-28

Family

ID=70740501

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21724301.3A Active EP4153680B1 (fr) 2020-05-18 2021-05-11 Mélange polycarbonate à brouillage réduit

Country Status (6)

Country Link
US (1) US20230220196A1 (fr)
EP (1) EP4153680B1 (fr)
KR (1) KR20230013029A (fr)
CN (1) CN115551944A (fr)
MX (1) MX2022014475A (fr)
WO (1) WO2021233727A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230163066A (ko) * 2022-05-23 2023-11-30 롯데케미칼 주식회사 열가소성 수지 조성물 및 이로부터 제조된 성형품

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3024210A (en) 1956-10-15 1962-03-06 Dow Corning Method of obtaining room temperature organopolysiloxane resin foams and product obtained therefrom
DE1495626B1 (de) 1960-03-30 1971-06-09 Bayer Ag Verfahren zum herstellen von polyestern
US3419634A (en) 1966-01-03 1968-12-31 Gen Electric Organopolysiloxane polycarbonate block copolymers
US3644574A (en) 1969-07-17 1972-02-22 Eastman Kodak Co Shaped articles of blends of polyesters and polyvinyls
US4013613A (en) 1971-10-01 1977-03-22 General Electric Company Reinforced intercrystalline thermoplastic polyester compositions
DE2232877B2 (de) 1972-07-05 1980-04-10 Werner & Pfleiderer, 7000 Stuttgart Verfahren zur Herstellung von Polyestern
JPS5292295A (en) 1976-01-29 1977-08-03 Sumitomo Chem Co Ltd Preparation of aromatic polyester
IT1116721B (it) 1976-04-02 1986-02-10 Allied Chem Copolimero bisfenolo a tereftalato carbonato lavorabili in massa fusa
DE2842005A1 (de) 1978-09-27 1980-04-10 Bayer Ag Polycarbonate mit alkylphenyl-endgruppen, ihre herstellung und ihre verwendung
JPS5594930A (en) 1979-01-10 1980-07-18 Sumitomo Chem Co Ltd Preparation of aromatic polyester by improved bulk polymerization process
DE2940024A1 (de) 1979-10-03 1981-04-16 Bayer Ag, 5090 Leverkusen Aromatische polyester, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von spritzgussartikeln, folien und ueberzuegen
DE3007934A1 (de) 1980-03-01 1981-09-17 Bayer Ag, 5090 Leverkusen Aromatische polyestercarbonate, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von spritzgussartikeln, folien und ueberzuegen
DE3334782A1 (de) 1983-04-19 1984-10-25 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von polydiorganosiloxanen mit hydroxyaryloxy-endgruppen
DE3738143A1 (de) 1987-11-10 1989-05-18 Bayer Ag Verwendung von redoxpfropfpolymerisaten zur verbesserung der benzinbestaendigkeit von thermoplastischen, aromatischen polycarbonat- und/oder polyestercarbonat-formmassen
DE3832396A1 (de) 1988-08-12 1990-02-15 Bayer Ag Dihydroxydiphenylcycloalkane, ihre herstellung und ihre verwendung zur herstellung von hochmolekularen polycarbonaten
US10487164B2 (en) 2009-04-08 2019-11-26 Techno Polymer Co., Ltd. Automobile interior part with reduced squeaking noises
JP6146890B2 (ja) 2010-08-27 2017-06-14 テクノポリマー株式会社 軋み音を低減した熱可塑性樹脂組成物製接触用部品
JP6050637B2 (ja) 2011-09-02 2016-12-21 テクノポリマー株式会社 軋み音低減用熱可塑性樹脂組成物及び軋み音低減構造体
WO2017186663A1 (fr) * 2016-04-27 2017-11-02 Covestro Deutschland Ag Masses moulées thermoplastiques antistatiques
CN110088195B (zh) * 2016-12-28 2022-09-06 科思创德国股份有限公司 具有好的低温韧性、高光泽度和高加工稳定性的组合物和热塑性模塑料
CN107353617B (zh) * 2017-06-29 2019-10-08 上海锦湖日丽塑料有限公司 具有降噪性能的pc/abs合金及其制备方法
CN111954687B (zh) * 2018-03-28 2022-12-27 科思创知识产权两合公司 用于生产具有提高的光泽度的模制品的组合物和热塑性模塑料
US20210009768A1 (en) 2018-04-05 2021-01-14 Ddp Specialty Electronic Materials Us 9, Llc Thermoplastic composition

Also Published As

Publication number Publication date
WO2021233727A1 (fr) 2021-11-25
KR20230013029A (ko) 2023-01-26
US20230220196A1 (en) 2023-07-13
MX2022014475A (es) 2022-12-13
EP4153680A1 (fr) 2023-03-29
CN115551944A (zh) 2022-12-30

Similar Documents

Publication Publication Date Title
EP1527138B1 (fr) Matieres de moulage ignifuges a base de polycarbonate
EP2898002B1 (fr) Production d'un mélange de polyoléfine et d'organopolysiloxane
EP2513216B1 (fr) Compositions de polycarbonate à mouler ii résistant aux rayures et au choc, ayant de bonnes propriétés mécaniques
EP2382269B1 (fr) Compositions de polycarbonate résistant au choc, ignifugées
EP2125952B1 (fr) Compositions de polycarbonate à résilience modifiée
EP2181153B1 (fr) Matières moulables en polycarbonate chargé de fibres de verre
CN109863203B (zh) 包含滑石的聚碳酸酯组合物
WO2008061643A1 (fr) Compositions de polycarbonate chargées et modifiées choc
DE102009059075A1 (de) Flammgeschützte, schlagzähmodifizierte, kratzfeste Polycarbonat-Formmassen mit guten mechanischen Eigenschaften
EP4153680B1 (fr) Mélange polycarbonate à brouillage réduit
EP2291451A1 (fr) Compositions de polycarbonate à modification choc
KR20200135956A (ko) 향상된 광택의 성형물을 제조하기 위한 조성물 및 열가소성 성형 배합물
CN112218910A (zh) 包含粘滑改性剂母料的热塑性组合物
EP1910469B2 (fr) Procedes de production de compositions de polycarbonate a resilience modifiee
EP2382266B1 (fr) Compositions de polycarbonate à résilience modifiée
WO2019193192A1 (fr) Composition thermoplastique
EP2513217B1 (fr) Compositions de polycarbonate à mouler i résistant aux rayures et au choc, ayant de bonnes propriétés mécaniques
EP3307827A1 (fr) Masses à mouler en polycarbonate renforcé de fibres dotées d'une meilleure résistance au choc
US11174384B2 (en) Polycarbonate composition and polycarbonate molding material having improved flowability
DE10254549A1 (de) Flammwidrige Polycarbonat-Formmassen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20221219

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20231124

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502021002835

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN